Photographic element having removable antihalation layers



9 July 14,` 1942. J, R. WEBER f 2,289,397

` PHOTOGRAPHIC ELEMENTS HAVING REMQVABLE ANTIHALATION LAYERS Filed' Dec. 26, 17939 i Light sensitive layer Transpdrent Base Hnti-halation Layer Containing Soap-like anthraquino'ne dyes Patented July 14, 1942 UNITED STATE PATENT FOFFICE .mesne assignments, to E. L dulPont de Nemours i &'Company,wilmington', Del.;a corporation of Delawafe v 45"Clain |s. This invention-relates to novel anti-halation "layers foi photographic elements.- VMore particu jlarly' it relates toflight sensitive .photogra'pl'iic` film elements bearing a removable anti-halation layer composed of ai high'v molecular `.weight binding agent and adyelwhich exhibits soapflikeprop- "ertiesL y. 1. The inventionhas "for an object-*the preparadyes. The condensation product Voi rosailinetrisulfonic acid with lauric acidchlorideis repre- .sentative of `this class of dyes. flhelauroyl group maybe substituted by other carboxylic acidfacyl `groups, e.; g., of kfatty acids/of 12 to V18 carbon :atoms or `with .the corresponding 'sulphonyl raditionof'a new'andir'nproved anti-halationphoto-- @graphic element; :A `further objectisthepreparation Aof yimproved'renfiovable anti-halation llayers which donot' rfequirethe presence o fsur-fa'ce- `'active 'agents to 'Aiacilitate their removal.

This invention has for. a. -further objectztlie-v preparation of photographic elements which bear pan anti-halationllayer which :may befreadily renioved iin aqueous baths; A further object isgthe `-itireparation of fanti-halation layers which do not form colored .particles uponlbeingV mechanica11y, f

Y stressed. Astill further object isfthe production of. anti-halation layers which are` stable upon storage under humid conditionsandl do not deteriorateior: become tacky.' A still .further `object isV the preparation 'of photographic iilms whichdo not aiect. the f sensitivity of; `photographic rilm emulsion layers in Contact therewith. Still f urther objects will appear hereinafter.,`

The above and other objects are accomplished have sometimes `been referred toV as soap-like Wool dyes. Some of these dyes are recent in origin. So far as Iarn aware they have been used fora. few selected textileuses only. They arenot confinedV to any` one specic class oi com'- pounds, but on the contrary, are quite diverse in ichara'cten Thus, they may be'polyaryl r'neth'ane, ""azine, 'xanthene, acridine, anthraquinonegthiazine", etc., and azo dyestuis. y g The dyes in general contain'v at least one and preferably a plurality of benzenenuclei.' One or f morebenzen'e `nuclei in general contain one or more solubilizinggroups, preferably sulfonic acid Vgronps; I The'ibenzene generally containa subs'tituted or unsubstituted `lflydrocarbon) radical of the" aliphatic or alicyclic` series. :These groups produce 'substantivit y. l The hydrocarbon radicalsfmayibe directlyjoinedv to the benzenenuclei i or through various bridging radicals, e; g. 'amide l'linkages including carboxylic acid amide and sulfonic'a'cid amide linkages. The radicals may vary :considerably in carbon content, for instance, from 6 to 20-`or more carbon atoms, and preferably -from'l`2 to 18 carbon atoms. v.

Avpreferreduclass ofsoap-like dyes are the suitable dyes of this andother ca ls from iong chain'saturatedfaliplia?S1f0nic acids of 12 to 18 carbn atoms;n Otheruspelcmc .types x arejdisformula:

wherein R1 stands for-a substituent taken, from Suitable anthraquinone ,dyestuifs ,wherein the .long chainhydrocarbon radical "is Aattached 'to' a carboxyl group are describedin UQS. Patent 2,100,392. These compounds have the'"gener`al VVthe class consisting Iof OH, aminoand alkylarnino,

'Rzis an alkyl'or` alkenylradical or 8 to ZOcar-bon atoms, preferably `12 to,.18 carbon atoms, andin which there is at least onesulfonate group.4 By sulfonate groupismeant free sulfonic acid group -or -a water soluble salt thereof.

Specific dyes ,ofg-y the above type are Alamine-1.1.-

- m-.carbododecoxyanilinoanthraquinone 2 `sul- `fonic v acid, .lfamino-bocarbododecoxyalinoanthraquinone-Z-sulfonic acid, llmethyl-amino-io 1 carbododecoxyanilinoanthraquinonesulfonic anilinoanthraquinonesulfonic acid, 1 amino-2.- inethyl`45ocarbododecoxyanilinoanthraquinone, 1 amino -4-m carbodecyloxyanilinoanthraquinone 2 s ulfonic acid,` 1-amino-4-m-carbo- I-oleyloxyanilinoanthraquinone-2-su1fonic acid, 1-

sulfonic acid, 1hydroxy4-m-carboxyanilinoanthraquinonesulfonlc acid, 2-bromo-1-amino- 4 mcarbododecoxyanilinoanthraquinone-6-sulfonic acid, and 1eamino-4-carbododecoxyanilinoanthraquinone-2:6-disulfonic acid.

A further class of suitable and somewhatrelated -anthraquinone type dyes in. whichthe long `chain aliphatic hydrocarbon radicals are attached .directly to an aromatic` hydrocarbon nucleus are described in U. S. Patent 2,100,392.

These dyes have the general formula: g" `Aq---X-R.'Ja` n wherein Amstands for an Qanthraquinone radical; X stands for a linkingradical of the class cono sisting of -NH-, -0 and '-`-S-';'R is an arylene radical of the class consisting of phenylene, naphthalene and acenaphthylene, and

R is a long chain alkyl or alkenyl group of 8 to 2O and preferably 12 to 18 carbon atoms which are further characterized in that at least one aromatic nucleus contains at least one sulfonic acid group.

Specific dye compounds of the last-mentioned type include, 2-sulfonic-1-amino-4-(p-dodecyl) anilinoanthraquinone, 2-sulfonic-1-amino-4-(pcetylanilino)-anthranuinone and p-dodecylanilinoanthraquinonesulfonic acid, and their further sulfonated derivatives.

In the accompanying drawing a transparent support I has imposed on one face thereof alightysensitive layer 2, on the reverse f ace of this Support is imposed an antihalation layer 3 consisting of a binding agent having disposed therethrough as an antihalation material a soap-like anthraquinone type antihalation dye.

A still further class of suitable dyes are the azo type dyes which contain a longV chain alcohol hydrocarbon radical attached to a carboxyl group and are described in U. S. Patent 2,155,493. These I dyes. have the general formula:

I wherein X is the radical of a coupling component from the group consisting of naphthol monoand di-sulfonic acids, amino-naphthol monoand di-sulfonic acids, acylamino-naphthol monoand di-sulfonic acids, alkyl-amino-naphthol monoand di-sulfonic acids, pyrazolone sulfonic acids, pyrazolone carboxylic acids, and the halogen derivatives of said acids; Ar is the residue of benzene; Y is one of a group consisting of hydrogen, methyl, methoxy and chloro; and R is a long chain aliphatic hydrocarbon radical of 8 to 20 and preferably 12 to 18 carbon atoms.

Specific dyes of the type just described may be made from the following components:

Diazo component Coupling component Cetyl-m-aminobenzoate Dodecyl 3-axnlno4-methoxyl-benzoate. naphthol--sulphonic acid (alkaline colpled):

Do l( :5d1chloro4sulphopheny1)-3- methyl-pyra'zolone. Do l-naphthol-BzG-disulphonic acid. Do 1(4sulphophenyl) 5- pyrazolone 3-carboxy1ic acid. Do 1-(4su1phophenyl) -3 methyl-5- r pyrazolone.

Do lbenzoylamlno- 8- naphthol- 3:6-

disulph'onic acid. Do 1-acetam1no-8naphtho1-4:6-disu1 phonic acid. Do 2- N- acetyl- N-- hydroxy ethylacid. Dodecyl 2- chloro -5- amino 1 acetamino e 8 naphthol 4:6

1-benzoate. disulphonic acid.

l-naphthol-S:6-disulphonic acid.

1 acetamino 8 naphthol 4:6

disulphonic acid.

l-naphthol-3z-disulphonic acid.

o Decyl-p-amino-benzoate Dodecyl-S-amino-4 methoxy- 1-benzoate.

of blue sensitive -and orthochromatic emulsions can be minimized by the use of black and red non-halation layers. Panchromatic emulsions, theoretically, require black non-halation layers although'green and deep blue can be used advantageously. Mixtures of dyes to produce various shades are sometimes desirable.

The binding agents for the anti-halation layers as previously stated can be water soluble proteins, e. g. gelatine, water-,soluble cellulose derivatives including water-solublel cellulose ethers, e. g. methyl cellulose, ethyl cellulose, etc., watersoluble cellulose esters including the water-soluble salts of the dicarboxylic acid esters of cellulose, e. g. the alkali metal ammonium and lower alkyl and mono, di and tri-ethanolamine salts of cellulose phthalate, cellulose acetate phthalate, cellulose succinate; and the same salts of cellulose glycollate, cellulose diglycollate, etc.; polyvinyl alcohol; partially hydrolyzed polyvinyl esters; polymeric amino-nitrogen containing bodies of Dawson Serial No. 245,528, led December 13, 1938; water-soluble salts of polyglucuronic acid, e. g. ammonium polyglucuronate. Protective coatings may in some instances be added, such as rosin, casein, etc., if desired.

The binding agents are dissolved in an aqueous or aqueous-organic solvent bathand the dye of the above-described type which exhibits soaplike properties added thereto preferably from a solvent solution. The resulting coating solution is then coated on the support of the photographic element and dried. The dye is of such tinctorial strength or is added in suflicient amounts to stop the passage of light rays. The coating solution may be water alone or water in admixture with a water-miscible `solvent such as methanol,

ethanol, acetone, etc. In general, the dye ls rst Water ccs-- 800 Ethyl alcohol ccs-- 200 Ethyl cellulose grams-- 20 Palmitoyl amino phenonaphthazoxoniumsodium-disulphonate grams-- 16 was prepared by adding the ethyl cellulose to water and then the dye'with agitation. The blue dye was first dissolved in ethanol. The slightly viscous mixture obtained thereby was coated on to the reverse side of a transparent cellulose nitrate film base which carried upon its face a panchromatic emulsiomby means of a beading roller and allowed to dry.

The resulting film was smooth, uniform, and

Afree from repellent spots and coating streaks. It

was found to have excellent anti-halationcharacteristics and was free from tackiness.

' readily removable in alkaline developer baths.

Similar amounts of the following give similar results: lauroyl-rosaniline-trisulfonic acid sodium salt (purple), the addition product of dimethylv sulfate to lauroyl neutral red (red), myristoylfluorescein-tetra sulfonic acid sodium salt (yel- It was l iowi' and undecyi asymmfdimethyl-thionine (blue). v v

y Example Il lwas prepared ina similar, manner to Example I and similarly Vcoated upon a cellulose acetate lm base whichcontained on itsV face a panchromatic emulsion. Thefilm had the samel .v properties and characteristics as that described in Example I.

Y Example `111 Acoating solution having the following composition: l

Water ;Q cubic centimeters 300 Gelatine r grarns `v 15 2-sulfonic-1amino'4 (p-cetyl-aniline) -an- -thraquinone grams.- "3

was prepared in the. following manner. Fifteen grams of gelatine were vswollen in cold water, subsequently melted and then the liquid volume made up to 300 ccs. with additional warm water and the dye added with agitation. The dye was first dissolved in a little ethanol. The slightly viscous vmixture obtained thereby was coated on `to the back side of a transparent cellulose nitrate film base which carried upon its face a panchromatic emulsion, by 'means of a beading roller and allowed to dry. `z

.The resulting lm was smooth, uniform and I free fromrepllent spots and coating streaks. vIt was found to have excellent anti-halation` characteristics and was free from tackiness.

' The layer `was removed' in an alkaline metol` hydroquinone developing solution.

i 3 emulsions which contain sensitizers such as cyanine, carbocyanine, pseudo-cyanine, cyazine bases and salts. That is, it must be absorptive Vof light of the wave lengths to which the emul- `sion ispredoininately sensitive. In4 general the dye should,be `added in an amount suiiicient to give a photometric density of 0.8 or the amount of dyed layer'should besuiiicient to give such a density.

Ihe soap-like dyes have a number of decided ,advantages in antihalation coatings. Since they are substantive to various binders and yespecially to gelatine, they .willnot migrate to a ,gelatine emulsion in close contact withV the non-halation backing.. This 'is of importance when film is spooled inrolls yincluding daylight loading film, or packed in sheets face-to-face.

VA 4further advantage results from their soap `v f like nature whereby. they act as a surface lubrideparting from the spirit and scope thereof, it is to be understood( that I doy not limit myself to the specific embodiments herein except as der fined `by the appended claims.`

Ir'rplaoel of the specific soap-like v.dye described e in this and the following examples may be substituted any suitable dye herein described or referred to.

Example IV Polyvinyl alcohol-; cgrams 40 Y Dye prepared from `cetylm-aminobenzo ate and l-amino-S-naphthol-3,6-di-sulf fonic acid grams 40 Water ;Cubic centimeters 20.00 Alcoho`l do f 500 The polyvinyl alcohol and dye were added to the water, alcohol mixture. The slightly viscous mixture obtained thereby was coated on to the reverse side of a transparent cellulosic film base which contained upon its face a panchromatic emulsion, by means of a beading roller and allowed to dry. i

The resulting film was very smooth and uniform and free from coating streaks and repellent spots. It was found to have excellent anti-halavtion characteristics and was free from tackiness.

The anti-halation layer, after exposure of the.

film, was rapidly dissolved from the film base by ordinary metol-hydroquinone-carbonate devel-` opers. Y The dye or mixture as stated above to be used 'in any specific instance is primarily'determned by the light sensitivity ofv the emulsion. Such `emulsions are usually gelatin silverlhalide, `e. g.

silver chloride, silver bromide, silver iodide, silver Calende-bromide, suver bromide-iodide, etc.

I claimt 1. A photographic element comprising a transparent base,a gelatine silver halide emulsion on one side of the base and an anti-halaton layer on the other side of the base composed of a water soluble high molecular weight binding agent and a dye having soap-like properties which is absorptive of the rays to which the coating is' sensitized having the general formula:

, hoort.

wherein R1 is amember ofthe group consisting off-H, -OH, NH2 and alkylamino, R2 is a hydrocarbon radical taken from the class consisting of alkyl and alkenyl radicals of 8 to20 carbon atoms, at least one of the benzene nuclei l containing a sulfonate group.

2. A photographic element comprising a transparent base, a gelatino silver chloride emulsion on one side of the b ase and an anti-halation layer on the other side of the base composed of a water soluble high molecular weight binding agent and a dye having soap-like properties which is absorptive of the rays to which the coating is sensitized having the general formula:

HN- I K hook, wherein Ri is4 a member ofthe group'consisting lon ol' -H, -OH, -NHz and alkylarnino, Rz is a hydrocarbon radical takenY from the class consisting of alkyl 'and alkenyl radicals of 8 `1:0720 carbon at'on'is,`at least one of the benzene nuclei containing a sulfonate group. A' y 3. A photographic element comprising a transone side of the base and an lariti-halation layer thevother side` of4 the base composed of va water-soluble high molecular weight binding Aparent base, a gelatin'o silver halide emulsion on agent and a dye having soap-like properties which is absorptive of the'rays to which the coating is `sensitized having thegene'ral formula:

Aq-X-RR v` r wherein Aq isvan anthraqunone radical, X is'a linking radicall taken froml the class consisting of -NH-, 0 3 and S R' is an arylene radical taken from the 'class'consisting of -phenylene, naphthalene andacenaphthaleneand R is a hy- `tlrocfarbon radical taken'from the class consistingof'alkyl 'and alkenyl radicals of 8 to 20 carbon atoms, at least 'one of the benzene nucleicon tair'iing a 4sulfonate group.

4.' A photographic element comprising a transparent base,` a gelatino silver chloride emulsion on one side of the base and an anti-halation layer on the other side of the base composed of a water-*soluble high molecular weight binding agent and a dye having soap-like properties which ls absorptive of the rays to which the coating @is sensitized having the general formula:

one side of the base and an anti-halation llayer on the other side of the base composed of a water-soluble high molecular weight binding agent, and a dye 4having soap-like properties which is absorptive of the rays to which the coating -iscsensitizedhaving the' general formula:

RooC-Ar-Ny-x wherein X is the radical ofl a coupling component from the group consisting of naphtholmonoand di-sulfonic acids, amino-naphthol mono-l and di- 'sulfonic acids, acylamino-naphthol mono and di-sulfonic acids, alkyl-amino-naphthol mono-l and di-sulfonic acids, pyrazolone sulfonicV acids,

f pyrazolone carboxylic acids, and the halogen derivatives of said acids; Ar is the residue of benzene; Y is one of a group .consisting of hydrogen,

methyl, methoxy and chloro; vand R is along chain aliphatic hydrocarbon radical of 8 to 20 and preferably 12 to v18 carbon atoms.`

JOHN afm/EBEE. 

